U.S. patent application number 13/870080 was filed with the patent office on 2013-10-31 for production of alpha, omega-diols.
This patent application is currently assigned to E I DU PONT DE MEMOURS AND COMPANY. The applicant listed for this patent is E I DU PONT DE MEMOURS AND COMPANY. Invention is credited to Alan Martin Allgeier, Wathudura Indika Namal De Silva, Carl Menning, Joachim C. Ritter, Sourav Kumar Sengupta.
Application Number | 20130289312 13/870080 |
Document ID | / |
Family ID | 48325948 |
Filed Date | 2013-10-31 |
United States Patent
Application |
20130289312 |
Kind Code |
A1 |
Allgeier; Alan Martin ; et
al. |
October 31, 2013 |
PRODUCTION OF ALPHA, OMEGA-DIOLS
Abstract
Disclosed herein are processes for preparing an
.alpha.,.omega.-C.sub.n-diol, wherein n is 5 or greater, from a
feedstock comprising a C.sub.n oxygenate. In some embodiments, the
process comprises contacting the feedstock with hydrogen gas in the
presence of a catalyst comprising metals M1, M2, and M3 and
optionally a support, wherein: M1 is Mn, Cr, V, or Ti; M2 is Ni,
Co, or Fe; and M3 is Cu, Ag, Pt, Pd or Au; or M1 is Pt or Rh; M2 is
Cu, Ni or Pd; and M3 is Mo, Re or W. The C.sub.n oxygenate may be
obtained from a biorenewable resource.
Inventors: |
Allgeier; Alan Martin;
(Wilmington, DE) ; De Silva; Wathudura Indika Namal;
(Wilmington, DE) ; Menning; Carl; (Newark, DE)
; Ritter; Joachim C.; (Wilmington, DE) ; Sengupta;
Sourav Kumar; (Wilmington, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE MEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Assignee: |
E I DU PONT DE MEMOURS AND
COMPANY
Wilmington
DE
|
Family ID: |
48325948 |
Appl. No.: |
13/870080 |
Filed: |
April 25, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61639449 |
Apr 27, 2012 |
|
|
|
Current U.S.
Class: |
564/511 ;
568/861 |
Current CPC
Class: |
B01J 21/063 20130101;
C07C 209/16 20130101; B01J 37/0201 20130101; B01J 23/8986 20130101;
B01J 2229/186 20130101; C07C 29/60 20130101; B01J 23/8993 20130101;
B01J 29/76 20130101; B01J 29/78 20130101; C07C 209/16 20130101;
B01J 37/0205 20130101; B01J 37/0036 20130101; B01J 23/8892
20130101; C07C 31/20 20130101; C07C 211/12 20130101; B01J 23/6567
20130101; B01J 23/868 20130101; B01J 23/6527 20130101; B01J 35/023
20130101; B01J 29/74 20130101; C07C 29/60 20130101 |
Class at
Publication: |
564/511 ;
568/861 |
International
Class: |
C07C 29/60 20060101
C07C029/60; C07C 209/16 20060101 C07C209/16 |
Claims
1. A process for preparing an .alpha.,.omega.-C.sub.n-diol,
comprising the steps: (a) providing a feedstock comprising a
C.sub.n oxygenate; and (b) contacting the feedstock with hydrogen
gas, in the presence of a catalyst at a temperature and for a time
sufficient to form a product mixture comprising an
.alpha.,.omega.-C.sub.n-diol, wherein n is 5 or greater; and
wherein the catalyst comprises metals M1, M2, and M3, and
optionally a support, wherein M1 is Mn, Cr, V, or Ti; M2 is Ni, Co,
or Fe; and M3 is Cu, Ag, Pt, Pd or Au; or M1 is Pt or Rh; M2 is Cu,
Ni or Pd; and M3 is Mo, Re or W.
2. The process of claim 1, wherein n=5 or 6.
3. The process of claim 1, wherein the optional support is present
in the catalyst and comprises WO.sub.3, SiO.sub.2, Al.sub.2O.sub.3,
carbon, TiO.sub.2, ZrO.sub.2, SiO.sub.2--Al.sub.2O.sub.3,
montmorillonite, SiO.sub.2--TiO.sub.2, tungstated ZrO.sub.2,
zeolites, V.sub.2O.sub.5, MoO.sub.3, or mixtures thereof.
4. The process of claim 1, wherein the C.sub.n oxygenate comprises
1,2,6-hexanetriol; 1,2,5-pentanetriol;
2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;
furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol;
levoglucosenone; levoglucosan; levoglucosenol;
1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide;
hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol;
3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol;
1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol;
5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl
alcohol; tetrahydrofurfuryl alcohol; pentoses; dimers containing
pentose; oligomers containing pentose; hexoses; dimers containing
hexose; oligomers containing hexose; condensation products from the
reaction of 5-(hydroxymethyl)-2-furfural with ketones and/or
aldehydes; and condensation products from the reaction of furfural
with ketones and/or aldehydes.
5. The process of claim 4, wherein the C.sub.n oxygenate comprises
1,2,6-hexanetriol; 2H-tetrahydropyran-2-methanol;
tetrahydrofuran-2,5-dimethanol; levoglucosenone;
3,4-dihydro-2H-pyran-2-carbaldehyde, or mixtures thereof.
6. The process of claim 5, wherein the C.sub.n oxygenate comprises
1,2,6-hexanetriol.
7. The process of claim 4, wherein the C.sub.n oxygenate comprises
1,2,5-pentanetriol; furfural; furfuryl alcohol; tetrahydrofurfuryl
alcohol; xylitol; or mixtures thereof.
8. The process of claim 1, wherein M1 is Mn, Cr, V, or Ti; M2 is
Ni, Co, or Fe; and M3 is Cu, Ag, Pt, Pd or Au.
9. The process of claim 8, wherein M1 is Mn or Cr; M2 is Ni, Co, or
Fe; and M3 is Cu.
10. The process of claim 1, wherein M1 is Pt or Rh; M2 is Cu, Ni or
Pd; and M3 is Mo, Re or W.
11. The process of claim 10, wherein M1 is Pt or Rh; M2 is Cu or
Ni; and M3 is Re or W.
12. The process of claim 3, wherein the support comprises
TiO.sub.2, a zeolite, or mixtures thereof.
13. The process of claim 1, further comprising the steps: (c)
optionally, isolating the .alpha.,.omega.-C.sub.n-diol from the
product mixture; (d) contacting the .alpha.,.omega.-C.sub.n-diol
with ammonia and hydrogen in the presence of a reductive amination
catalyst at a temperature and for a time sufficient to form a
second product mixture comprising an
.alpha.,.omega.-C.sub.n-diaminoalkane; and (e) optionally,
isolating the .alpha.,.omega.-C.sub.n-diaminoalkane from the second
product mixture.
14. The process of claim 13, wherein the
.alpha.,.omega.-C.sub.n-diaminoalkane comprises 1,6-diaminohexane.
Description
[0001] This application claims priority under 35 U.S.C.
.sctn.119(e) from, and claims the benefit of U.S. Provisional
Application No. 61/639,449 filed Apr. 27, 2012, which is by this
reference incorporated in its entirety as a part hereof for all
purposes.
FIELD OF DISCLOSURE
[0002] The present invention relates to processes for preparing
alpha, omega-diols (".alpha.,.omega.-diols"). More particularly,
the present invention relates to processes for preparing
.alpha.,.omega.-diols by selective hydrodeoxygenation of oxygenated
compounds which can be derived from carbohydrates or biologic
sources.
BACKGROUND
[0003] Alpha, omega-diols such as 1,5-pentanediol and
1,6-hexanediol are useful as chemical intermediates for the
production of, e.g., agrichemicals, pharmaceuticals, and polymers.
For example, .alpha.,.omega.-diols can be used as plasticizers and
as comonomers in polyesters and polyether-urethanes. It has become
increasingly desirable to obtain industrial chemicals such as
.alpha.,.omega.-diols, or their precursors, from materials that are
not only inexpensive but also benign in the environment. Of
particular interest are materials which can be obtained from
renewable sources, that is, materials that are produced by a
biological activity such as planting, farming, or harvesting. As
used herein, the terms "renewable" and "biosourced" can be used
interchangeably.
[0004] Biomass sources for such materials are becoming more
attractive economically versus petroleum-based ones. Although the
convergent and selective synthesis of C.sub.5 and C.sub.6
carbocyclic intermediates from biomass is difficult because of the
high degree of oxygenation of many components of biomass, use of
such biomass-derived intermediates as feedstocks would offer new
routes to industrially useful chemicals.
[0005] 1,6-Hexanediol is a useful intermediate in the industrial
preparation of nylon 66. 1,6-Hexanediol can be converted by known
methods to 1,6-hexamethylene diamine, a starting component in nylon
production. 1,6-Hexanediol is typically prepared from the
hydrogenation of adipic acid or its esters or the hydrogenation of
caprolactone or its oligomers. For example, in WO 2011/149339,
deVries J-G, et al describe a process for the preparation of
caprolactone, caprolactam, 2,5-tetrahydrofuran-dimethanol,
1,6-hexanediol or 1,2,6-hexanetriol from
5-hydroxymethyl-2-furfuraldehyde and teach that 1,2,6-hexanetriol
may be hydrogenated to 1,6-hexanediol using a catalyst based on
palladium, nickel, rhodium, ruthenium, copper and chromium or
mixtures thereof. Further, the catalysts may be doped with one or
more other elements, such as rhenium.
[0006] JP 2003-183200 teaches a method for preparation of
2,5-diethyl-1,6-hexanediol from tetrahydropyran derivatives, e.g.
2,5-diethyltetrahydropyran-2-methanol, comprising hydrogenation of
the starting material in the presence of a metal catalyst carried
on an acidic support, notably 5% Pt/Al.sub.2O.sub.3 and 5%
Pt/SiO.sub.2--Al.sub.2O.sub.3 at 200-240.degree. C. Yields ranged
from 40 to 61%.
[0007] There is an existing need for processes to make
.alpha.,.omega.-diols, especially C.sub.5 and C.sub.6
.alpha.,.omega.-diols, and synthetic intermediates useful in the
production of .alpha.,.omega.-diols, from renewable biosources.
There is an existing need for processes to produce 1,5-pentanediol,
1,6-hexanediol, and other .alpha.,.omega.-diols at high yield and
high selectivity from biomass-derived starting materials, including
1,2,6-hexanetriol, tetrahydrofuran-2,5-dimethanol, and
2-hydroxymethyltetrahydropyran.
SUMMARY
[0008] In one embodiment, a process for preparing an
.alpha.,.omega.-C.sub.n-diol is provided, the process comprising
the steps:
[0009] (a) providing a feedstock comprising a C.sub.n oxygenate;
and
[0010] (b) contacting the feedstock with hydrogen gas, in the
presence of a catalyst at a temperature and for a time sufficient
to form a product mixture comprising an
.alpha.,.omega.-C.sub.n-diol, wherein n is 5 or greater; and
wherein the catalyst comprises metals M1, M2, and M3 and optionally
a support, wherein:
[0011] M1 is Mn, Cr, V, or Ti; M2 is Ni, Co, or Fe; and M3 is Cu,
Ag, Pt, Pd or Au; or
[0012] M1 is Pt or Rh; M2 is Cu, Ni or Pd; and M3 is Mo, Re or
W.
[0013] In one embodiment, the optional support is present in the
catalyst and comprises WO.sub.3, SiO.sub.2, Al.sub.2O.sub.3,
carbon, TiO.sub.2, ZrO.sub.2, SiO.sub.2--Al.sub.2O.sub.3,
montmorillonite, SiO.sub.2--TiO.sub.2, tungstated ZrO.sub.2,
zeolites, V.sub.2O.sub.5, MoO.sub.3, or mixtures thereof. In one
embodiment, the support comprises TiO.sub.2, a zeolite, or mixtures
thereof.
[0014] In one embodiment, the C.sub.n oxygenate comprises
1,2,6-hexanetriol; 1,2,5-pentanetriol;
2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;
furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol;
levoglucosenone; levoglucosan; levoglucosenol;
1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide;
hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol;
3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol;
1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol;
5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl
alcohol; tetrahydrofurfuryl alcohol; pentoses; dimers containing
pentose; oligomers containing pentose; hexoses; dimers containing
hexose; oligomers containing hexose; condensation products from the
reaction of 5-(hydroxymethyl)-2-furfural with ketones and/or
aldehydes; and condensation products from the reaction of furfural
with ketones and/or aldehydes.
[0015] In one embodiment, the process further comprises the
steps:
[0016] (c) optionally, isolating the .alpha.,.omega.-C.sub.n-diol
from the product mixture;
[0017] (d) contacting the .alpha.,.omega.-C.sub.n-diol with ammonia
and hydrogen in the presence of a reductive amination catalyst at a
temperature and for a time sufficient to form a second product
mixture comprising an .alpha.,.omega.-C.sub.n-diaminoalkane;
and
[0018] (e) optionally, isolating the
.alpha.,.omega.-C.sub.n-diaminoalkane from the second product
mixture.
DETAILED DESCRIPTION
[0019] As used herein, where the indefinite article "a" or "an" is
used with respect to a statement or description of the presence of
a step in a process of this invention, it is to be understood,
unless the statement or description explicitly provides to the
contrary, that the use of such indefinite article does not limit
the presence of the step in the process to one in number.
[0020] As used herein, when an amount, concentration, or other
value or parameter is given as either a range, preferred range, or
a list of upper preferable values and lower preferable values, this
is to be understood as specifically disclosing all ranges formed
from any pair of any upper range limit or preferred value and any
lower range limit or preferred value, regardless of whether ranges
are separately disclosed. Where a range of numerical values is
recited herein, unless otherwise stated, the range is intended to
include the endpoints thereof, and all integers and fractions
within the range. It is not intended that the scope of the
invention be limited to the specific values recited when defining a
range.
[0021] As used herein, the terms "comprises," "comprising,"
"includes," "including," "has," "having," "contains" or
"containing," or any other variation thereof, are intended to cover
a non-exclusive inclusion. For example, a composition, a mixture,
process, method, article, or apparatus that comprises a list of
elements is not necessarily limited to only those elements but may
include other elements not expressly listed or inherent to such
composition, mixture, process, method, article, or apparatus.
Further, unless expressly stated to the contrary, "or" refers to an
inclusive or and not to an exclusive or. For example, a condition A
or B is satisfied by any one of the following: A is true (or
present) and B is false (or not present), A is false (or not
present) and B is true (or present), and both A and B are true (or
present).
[0022] As used herein, the term "about" modifying the quantity of
an ingredient or reactant employed refers to variation in the
numerical quantity that can occur, for example, through typical
measuring and liquid handling procedures used for making
concentrates or use solutions in the real world; through
inadvertent error in these procedures; through differences in the
manufacture, source, or purity of the ingredients employed to make
the compositions or carry out the methods; and the like. The term
"about" also encompasses amounts that differ due to different
equilibrium conditions for a composition resulting from a
particular initial mixture. Whether or not modified by the term
"about", the claims include equivalents to the quantities. The term
"about" may mean within 10% of the reported numerical value,
preferably within 5% of the reported numerical value.
[0023] As used herein, the term "organic compound" means a
carbon-containing compound with the following exceptions: binary
compounds as the carbon oxides, carbides, carbon disulfide, etc.;
ternary compounds such as metallic cyanides, metallic carbonyls,
phosgene, carbonylsulfide; and metallic carbonates such as calcium
carbonate and sodium carbonate.
[0024] As used herein, the term "oxygenate" means an organic
compound containing at least one oxygen atom. As used herein, the
term .sup."C.sub.n oxygenate" means an oxygenate containing n
carbon atoms and, analogously, the term "C.sub.n diol" denotes a
diol containing n carbon atoms.
[0025] As used herein, the term "biomass" refers to any cellulosic
or lignocellulosic material and includes materials comprising
hemicellulose, and optionally further comprising lignin, starch,
oligosaccharides and/or monosaccharides.
[0026] As used herein, the term "lignocellulosic" means comprising
both lignin and cellulose. Lignocellulosic material may also
comprise hemicellulose. In some embodiments, lignocellulosic
material contains glucan and xylan.
[0027] As used herein, the term "hemicellulose" means a
non-cellulosic polysaccharide found in lignocellulosic biomass.
Hemicellulose is a branched heteropolymer consisting of different
sugar monomers. It typically comprises from 500 to 3000 sugar
monomeric units.
[0028] As used herein, the term "lignin" refers to a complex high
molecular weight polymer that can comprise guaiacyl units, as in
softwood lignin, or a mixture of guaiacyl and syringyl units, as in
hardwood lignin.
[0029] As uses herein, the term "starch" refers to a carbohydrate
consisting of a large number of glucose units joined by glycosidic
bonds. Starch, also known as amylum, typically contains amylose and
amylopectin.
[0030] As used herein, the term "sugar" includes monosaccharides,
disaccharides, and oligosaccharides. Monosaccharides, or "simple
sugars," are aldehyde or ketone derivatives of straight-chain
polyhydroxy alcohols containing at least three carbon atoms. A
pentose is a monosaccharide having five carbon atoms; examples
include xylose, arabinose, lyxose, and ribose. A hexose is a
monosaccharide having six carbon atoms; examples include glucose
and fructose. Disaccharide molecules consist of two covalently
linked monosaccharide units; examples include sucrose, lactose, and
maltose. As used herein, "oligosaccharide" molecules consist of
about 3 to about 20 covalently linked monosaccharide units. Unless
indicated otherwise herein, all references to specific sugars are
intended to include the D-stereoisomer, the L-stereoisomer, and
mixtures of the stereoisomers.
[0031] As used herein, the term "C.sub.n sugar" includes
monosaccharides having n carbon atoms; disaccharides comprising
monosaccharide units having n carbon atoms; and oligosaccharides
comprising monosaccharide units having n carbon atoms. Thus, the
term "C.sub.5 sugar" includes pentoses, disaccharides comprising
pentose units, and oligosaccharides comprising pentose units; the
term "C.sub.6 sugar" includes hexoses, disaccharides comprising
hexose units, and oligosaccharides comprising hexose units.
[0032] As used herein, the term "C.sub.n sugar alcohol" refers to
compounds produced from C.sub.n sugars by reduction of the carbonyl
group to a primary or secondary hydroxyl group. Sugar alcohols
having the general formula H(HCHO).sub.x+1H, are derived from
sugars having the general formula H(HCHO).sub.xHCO. Monosaccharides
and disaccharides can be used to form sugar alcohols, though the
disaccharides are not fully hydrogenated. Three examples of sugar
alcohols are xylitol (C.sub.5), sorbitol (C.sub.6), and mannitol
(C.sub.6).
[0033] As used herein, the abbreviation "16HD" refers to
1,6-hexanediol. The chemical structure of 1,6-hexanediol is
represented by Formula (I).
##STR00001##
[0034] As used herein, the abbreviation "15PD" refers to
1,5-pentanediol. The chemical structure of 1,5-pentanediol is
represented by Formula (II).
##STR00002##
[0035] As used herein, the abbreviation "126HT" refers to
1,2,6-hexanetriol and includes a racemic mixture of isomers. The
chemical structure of 1,2,6-hexanetriol is represented by Formula
(III).
##STR00003##
[0036] As used herein, the abbreviation "125PT''refers to
1,2,5-pentanetriol and includes a racemic mixture of isomers. The
chemical structure of 1,2,5-pentanetriol is represented by Formula
(IV).
##STR00004##
[0037] As used herein, the abbreviation "Tetraol" refers to
1,2,5,6-tetrahydroxyhexane, also known as 3,4-dideoxyhexitol, and
includes a mixture of stereoisomers. The chemical structure of
1,2,5,6-tetrahydroxyhexane is represented by Formula (V).
##STR00005##
[0038] As used herein, the abbreviation "Pentaol"refers to
1,2,3,5,6-hexanepentaol and includes a racemic mixture of isomers.
The chemical structure of 1,2,3,5,6-hexanepentaol is represented by
Formula (VI).
##STR00006##
[0039] As used herein, the abbreviation "THFdM" refers to
tetrahydro-2,5-furandimethanol (also known as
tetrahydrofuran-2,5-dimethanol or 2,5-tetrahydrofurandimethanol, or
2,5-bis[hydroxymethyl]tetrahydrofuran) and includes a mixture of
stereoisomers (cis and racemic trans isomers). The chemical
structure of tetrahydro-2,5-furandimethanol is represented by
Formula (VII).
##STR00007##
[0040] The chemical structure of 2,5-dihydrofuran-2,5-dimethanol is
represented by Formula (VIII).
##STR00008##
[0041] As used herein, the abbreviation "FdM" refers to
2,5-furandimethanol, also known as 2,5-bis(hydroxymethyl)furan. The
chemical structure of 2,5-furandimethanol is represented by Formula
(IX).
##STR00009##
[0042] The chemical structure of furfural, also known as
furan-2-carbaldehyde or 2-furaldehyde, is represented by Formula
(X).
##STR00010##
[0043] The chemical structure of hydroxymethylfurfural, also known
as 5-(hydroxymethyl)-2-furaldehyde, is represented by Formula
(XI).
##STR00011##
[0044] The chemical structure of furfuryl alcohol, also known as
2-furanmethanol, is represented by Formula (XII).
##STR00012##
[0045] The chemical structure of tetrahydrofurfuryl alcohol, also
known as tetrahydro-2-furanmethanol, is represented by Formula
(XIII).
##STR00013##
[0046] As used herein, the abbreviation "THPM" refers to
tetrahydro-2H-pyran-2-methanol, also known as
2-hydroxymethyltetrahydropyran, and includes a racemic mixture of
isomers. The chemical structure of tetrahydro-2H-pyran-2-methanol
is represented by Formula (XIV).
##STR00014##
[0047] As used herein, the abbreviation "HOTHPM" refers to
2-hydroxymethyl-5-hydroxytetrahydro-2H-pyran, also known as
5-hydroxy-2H-tetrahydropyran-2 methanol or
1,5-anhydro-3,4-dideoxyhexitol, and includes a mixture of
stereoisomers. The chemical structure of
2-hydroxymethyl-5-hydroxytetrahydro-2H-pyran is represented by
Formula (XV).
##STR00015##
[0048] The chemical structure of
3,4-dihydro-2H-pyran-2-carbaldehyde, also known as
3,4-dihydro-2H-pyran-2-carboxaldehyde,
2-formyl-3,4-dihydro-2H-pyran, or "acrolein dimer", is represented
by Formula (XVI).
##STR00016##
[0049] The chemical structure of levoglucosan, also known as
1,6-anhydro-.beta.-glucopyranose, is represented by Formula
(XVII).
##STR00017##
[0050] As used herein, the abbreviations "Lgone" and "LGone" refer
to levoglucosenone, also known as
1,6-anhydro-3,4-dideoxy-.beta.-D-pyranosen-2-one. The chemical
structure of levoglucosenone is represented by Formula (XVIII).
##STR00018##
[0051] The chemical structure of
1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one is represented by
Formula (XIX).
##STR00019##
[0052] The chemical structure of levoglucosenol, also known as
1,6-anhydro-3,4-dideoxy-.beta.-erythro-hex-3-enopyranose, is
represented by Formula (XX).
##STR00020##
[0053] As used herein, the abbreviations "Lgol" and "LGol" refer to
levoglucosanol, also known as 1,6-anhydro-3,4-dideoxyhexopyranose,
and include a mixture of the threo and erythro stereoisomers. The
chemical structure of 1,6-anhydro-3,4-dideoxyhexopyranose is
represented by Formula (XXI).
##STR00021##
[0054] As used herein, the abbreviation "ISOS" refers to
isosorbide, also known as 1,4:3,6-dianhydrosorbitol or
1,4-dianhydrosorbitol. The chemical structure of isosorbide is
represented by Formula (XXII).
##STR00022##
[0055] The chemical structure of sorbitol, also known as
hexane-1,2,3,4,5,6-hexol, is represented by Formula (XXIII).
##STR00023##
[0056] The chemical structure of glucose, also known as dextrose or
2,3,4,5,6-pentahydroxyhexanal, is represented by Formula
(XXIV).
##STR00024##
[0057] The chemical structure of fructose, also known as levulose,
is represented by Formula (XXV).
##STR00025##
[0058] The chemical structure of xylitol, also known as
pentane-1,2,3,4,5-pentol, is represented by Formula (XXVI).
##STR00026##
[0059] In one embodiment, a process is provided for preparing an
.alpha.,.omega.-C.sub.n-diol, the process comprising the steps:
[0060] (a) providing a feedstock comprising a C.sub.n oxygenate;
and
[0061] (b) contacting the feedstock with hydrogen gas, in the
presence of a catalyst at a temperature and for a time sufficient
to form a product mixture comprising an
.alpha.,.omega.-C.sub.n-diol, wherein n is 5 or greater; and
wherein the catalyst comprises metals M1, M2, and M3, and
optionally a support, wherein
[0062] M1 is Mn, Cr, V, or Ti; M2 is Ni, Co, or Fe; and M3 is Cu,
Ag, Pt, Pd or Au; or
[0063] M1 is Pt or Rh; M2 is Cu, Ni or Pd; and M3 is Mo, Re or
W.
[0064] In one embodiment, n=5 or 6. In one embodiment, n=5, and the
.alpha.,.omega.-C.sub.n-diol is 1,5-pentanediol. In one embodiment,
n=6, and the .alpha.,.omega.-C.sub.n-diol is 1,6-hexanediol. In one
embodiment, n=7, and the .alpha.,.omega.-C.sub.n-diol is
1,7-heptanediol. In one embodiment, n=8, and the
.alpha.,.omega.-C.sub.n-diol is 1,8-octanediol.
[0065] In one embodiment, the catalyst comprises metals M1, M2, and
M3 and optionally a support; wherein M1 is Mn, Cr, V, or Ti; M2 is
Ni, Co, or Fe; and M3 is Cu, Ag, Pt, Pd or Au. In one embodiment,
the catalyst comprises metals M1, M2, and M3 and optionally a
support; wherein M1 is Mn or Cr; M2 is Ni, Co, or Fe; and M3 is
Cu.
[0066] In one embodiment, the catalyst comprises metals M1, M2, and
M3 and optionally a support; wherein M1 is Pt or Rh; M2 is Cu, Ni
or Pd; and M3 is Mo, Re or W. In one embodiment, the catalyst
comprises metals M1, M2, and M3 and optionally a support; wherein
M1 is Pt or Rh; M2 is Cu or Ni; and M3 is Re or W.
[0067] Examples of C.sub.n oxygenates that are suitable for use in
the present processes include 1,2,6-hexanetriol;
1,2,5-pentanetriol; 2H-tetrahydropyran-2-methanol;
tetrahydrofuran-2,5-dimethanol; furan-2,5-dimethanol; 2,5
dihydrofuran-2,5-dimethanol; levoglucosenone; levoglucosan;
levoglucosenol; 1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one;
isosorbide; hydroxymethylfurfural; sorbitol; glucose; fructose;
xylitol; 3,4-dihydro-2H-pyran-2-carbaldehyde;
1,2,5,6-hexanetetraol; 1,2,3,5,6-hexanepentanol;
1,5-anhydro-3,4-dideoxy-hexitol; 5-hydroxy-2H-tetrahydropyran-2
methanol; furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol;
pentoses; dimers containing pentose; oligomers containing pentose;
hexoses; dimers containing hexose; oligomers containing hexose;
condensation products from the reaction of
5-(hydroxymethyl)-2-furfural ("HMF") with ketones and/or aldehydes,
and condensation products from the reaction of furfural with
ketones and/or aldehydes. The feedstock may comprise one or more Cn
oxygenates.
[0068] In one embodiment, the C.sub.n oxygenate comprises
1,2,6-hexanetriol; 2H-tetrahydropyran-2-methanol;
tetrahydrofuran-2,5-dimethanol; levoglucosenone;
3,4-dihydro-2H-pyran-2-carbaldehyde, or mixtures thereof. These
C.sub.n oxygenates are useful for preparation of reaction mixtures
comprising 1,6-hexanediol by the processes disclosed herein. In one
embodiment, the C.sub.n oxygenate comprises 1,2,6-hexanetriol.
[0069] In one embodiment, the C.sub.n oxygenate comprises
1,2,5-pentanetriol; furfural; furfuryl alcohol; tetrahydrofurfuryl
alcohol; xylitol; or mixtures thereof. These C.sub.n oxygenates are
useful for preparation of product mixtures comprising
1,5-hexanediol by the processes disclosed herein.
[0070] Examples of suitable pentoses include without limitation
xylose, arabinose, lyxose, xylitol, and ribose. Examples of
suitable hexoses include without limitation glucose, mannose,
fructose, and galactose. Examples of condensation products from the
reaction of furfural or 5-(hydroxymethyl)-2-furfural with ketones
and/or aldehydes are described in Synthesis (2008), (7), 1023-1028
(e.g., CAS Reg. No. 1040375-91-4 and CAS Reg. No. 886-77-1) ; and
in ChemSusChem (2010), 3(10), 1158-1161, in which subjecting
furfural and 5-(hydroxymethyl)-2-furfural to aldol condensation
produced molecules having 8 to 15 carbon atoms.
[0071] Suitable C.sub.n oxygenates can be derived from biorenewable
resources including biomass. Biomass may be derived from a single
source, or biomass can comprise a mixture derived from more than
one source; for example, biomass could comprise a mixture of corn
cobs and corn stover, or a mixture of grass and leaves. Biomass
includes, but is not limited to, bioenergy crops, agricultural
residues, municipal solid waste, industrial solid waste, sludge
from paper manufacture, yard waste, wood and forestry waste or a
combination thereof. Examples of biomass include, but are not
limited to, corn grain, corn cobs, crop residues such as corn
husks, corn stover, grasses, wheat, wheat straw, barley, barley
straw, hay, rice straw, switchgrass, waste paper, sugar cane
bagasse, sorghum, soy, components obtained from milling of grains,
trees, branches, roots, leaves, wood chips, sawdust, shrubs and
bushes, vegetables, fruits, flowers, and animal manure or a
combination thereof. Biomass that is useful for the invention may
include biomass that has a relatively high carbohydrate value, is
relatively dense, and/or is relatively easy to collect, transport,
store and/or handle. In one embodiment, the C.sub.n oxygenate is
ultimately derived from corn cobs, sugar cane bagasse, switchgrass,
wheat straw, sawdust and other wood waste, and lignocellulosic
feedstocks.
[0072] A biorenewable resource such as biomass can be pyrolyzed
under high temperature conditions in the presence of an acid
catalyst to provide useful chemical intermediates. For example,
pyrolysis of wood, starch, glucose or cellulose can produce
levoglucosenone by known and conventional methods (see, for
example, Ponder (Applied Biochemistry and Biotechnology, Vol 24/25,
41-41 (1990)) or Shafizadeh (Carbohydrate Research, 71, 169-191
(1979)).
[0073] Glycerol can be obtained from a biorenewable resource, for
example from hydrolysis of vegetable and animal fats and oils (that
is, triacylglycerides comprising ester functionality resulting from
the combination of glycerol with C.sub.12 or greater fatty acids).
1,2,6-Hexanetriol can be obtained from materials such as glucose,
cellulose or glycerol derived from a biorenewable resource. For
example, 1,2,6-hexanetriol can be obtained by a process comprising
the steps of contacting glycerol with a catalyst to prepare
acrolein, heating acrolein (optionally in the presence of a
catalyst) to prepare 2-formyl-3,4-dihydro-2H-pyran, contacting
2-formyl-3,4-dihydro-2H-pyran with water to prepare 2-hydroxyadipic
aldehyde and contacting 2-hydroxyadipic aldehyde with hydrogen and
a catalyst to produce a product mixture comprising
1,2,6-hexanetriol. See, for example, U.S. Pat. No. 2,768,213,
German Patent No. 4238493, and L. Ott, et al. in Green Chem., 2006,
8, 214-220.
[0074] The catalysts utilized in the process described herein can
be synthesized by any conventional method for preparing catalysts,
for example, deposition of metal salts from aqueous or organic
solvent solutions via impregnation or incipient wetness,
precipitation of an M1 component and/or an M2 component and/or an
M3 component, or solid state synthesis. Preparation may comprise
drying catalyst materials under elevated temperatures from
30-250.degree. C., preferably 50-150.degree. C.; calcination by
heating in the presence of air at temperatures from 250-800.degree.
C., preferably 300-450.degree. C.; and reduction in the presence of
hydrogen at 100-400.degree. C., preferably 200-300.degree. C., or
reduction with alternative reducing agents such as hydrazine,
formic acid or ammonium formate. The above techniques may be
utilized with powdered or formed particulate catalyst materials
prepared by tableting, extrusion or other techniques common for
catalyst synthesis. Where powdered catalysts materials are
utilized, it will be appreciated that the catalyst support or the
resulting catalyst material may be sieved to a desired particle
size and that the particle size may be optimized to enhance
catalyst performance.
[0075] The loading of M1 may be 0.1-50% but preferably 0.5-5% by
weight, based on the weight of the prepared catalyst (i.e.,
including the catalyst support where present). The loading of M2
may be 0.1-99.9%, for example 2-10%, or 0.5-5%. The loading of M3
may be 0.1-99%, for example 2-10%. Preferably the molar ratio of M1
to M2 to M3 in the catalysts is in the range of
0.1-1.0:0.1-1.0:1.0. Regarding the M1, M2, and M3 loadings, all
percentages are intended as weight percent relative to the total
weight of the prepared catalyst. In some embodiments, the molar
ratio of M1, M2, and M3 in the catalyst is such that M3/(M1+M2) is
from about 1.1:1 to about 1:1.1, for example about 1:1.
[0076] In some embodiments, it is useful to utilize a catalyst
which comprises a solid support to enhance the stability and
economic feasibility of the process. Examples of useful supports
include WO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, carbon, SiC,
TiO.sub.2, ZrO.sub.2, SiO.sub.2--Al.sub.2O.sub.3, clays such as
montmorillonite, SiO.sub.2--TiO.sub.2, tungstated ZrO.sub.2,
V.sub.2O.sub.5, MoO.sub.3, and zeolites such as H-Y, FAU (H-Y or
USY), BEA (H-Beta), MFI (H-ZSM5), MEL (H-ZSM11) and MOR
(H-Mordenite). Typically, tungstated ZrO.sub.2 can comprise up to
about 19 wt % Was WO.sub.3 on ZrO.sub.2, see for example S. Kuba et
al in Journal of Catalysis 216 (2003), p. 353-361. In one
embodiment, the catalyst further comprises a solid support
comprising WO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, carbon, TiO.sub.2,
ZrO.sub.2, SiO.sub.2--Al.sub.2O.sub.3, montmorillonite,
SiO.sub.2--TiO.sub.2, tungstated ZrO.sub.2,H-Y zeolites,
V.sub.2O.sub.5, MoO.sub.3, or mixtures thereof. In one embodiment,
the support comprises TiO.sub.2, a zeolite, or mixtures thereof. In
other embodiments, it may be desirable to not have a support.
[0077] The prepared catalyst can be in any physical form typical
for heterogeneous catalysts, including but not limited to powdered
(also known as "fluidized") forms with 0.01-150 .mu.m particle
size, formed tablets, extrudates, spheres, engineered particles
having uniform 0.5-10 mm size, monolithic structures on which
surfaces the catalyst is applied, or combinations of two or more of
the above. When a solid support is utilized, it is desirable that
M1 be intimately associated with the M2 component, the M3
component, or both, as measured by transmission electron microscopy
with energy dispersive spectroscopy. It is further preferable that
the particle size of the M1 component be less than 10 nm and most
preferably less than 3 nm as measured by the same techniques. In
this case, particle size of the M1 component may refer to that of a
mixture of the M1 and M2 components, an alloy of the M1 and M2
components, a particle of the M1 component adjacent to a particle
of the M2 component, or a particle of the M1 component on the
support which contains the M2 component.
[0078] The catalyst may be present in any weight ratio to the
feedstock sufficient to catalyze the selective hydrodeoxygenation,
generally in the range of 0.0001:1 to 1:1, preferably 0.001:1 to
0.5:1 for batch reactions. For continuous reactions, the same
ratios are appropriate where the weight ratio of feed to catalyst
is defined as weight of C.sub.n oxygenate feed processed per weight
of catalyst.
[0079] Useful temperatures for the processes are between about
30.degree. C. and about 300.degree. C. In some embodiments, the
temperature is between and optionally includes any two of the
following values: 30.degree. C., 40.degree. C., 50.degree. C.,
60.degree. C., 70.degree. C., 80.degree. C., 90.degree. C.,
100.degree. C., 110.degree. C., 120.degree. C., 130.degree. C.,
140.degree. C., 150.degree. C., 160.degree. C., 170.degree. C.,
180.degree. C., 190.degree. C., 200.degree. C., 210.degree. C.,
220.degree. C., 230.degree. C., 240.degree. C., 250.degree. C.,
260.degree. C., 270.degree. C., 280.degree. C., 290.degree. C., and
300.degree. C. It is expected that with some catalysts,
temperatures above about 300.degree. C. could be used.
[0080] The process is conducted by contacting a Cn oxygenate feed
with hydrogen in the presence of the catalyst for a time sufficient
to form a product mixture comprising an
.alpha.,.omega.-C.sub.n-diol. The mole ratio of hydrogen to feed is
not critical as long as sufficient hydrogen is present to produce
the desired .alpha.,.omega.-C.sub.n-diol. Hydrogen is preferably
used in excess, and may optionally be used in combination with an
inert gas such as nitrogen or argon. If an inert gas is used in
combination with the hydrogen, the amount of the inert gas should
be such that it does not negatively impact the formation of the
product mixture. The pressure of the process may be between about
300 kPa and about 25,000 kPa. In some embodiments, the pressure of
the process is between and optionally includes any two of the
following values: 300; 500; 1000; 1500; 2000; 2500; 3000; 3500;
4000; 4500; 5000; 10,000; 15,000; 20,000; and 25,000 kPa.
[0081] The process is typically conducted in the presence of a
solvent, which may serve to reduce the viscosity of the system to
improve fluidity of the catalyst in the reaction vessel and/or to
remove the heat of reaction and improve the performance of the
process. Polar solvents are preferred. The solvent may be present
in a range of 1% to 95% by weight of the total reaction mixture,
excluding the catalyst.
[0082] The reaction products may be isolated or purified by any
common methods known in the art including but not limited to
distillation, wiped film evaporation, chromatography, adsorption,
crystallization, and membrane separation.
[0083] It will be appreciated that the processes disclosed herein
can also be utilized to prepare useful intermediates or byproducts
in the synthesis of the .alpha.,.omega.-diols through optimization
of the process parameters. Examples of intermediates that can be
prepared during synthesis of 1,5-pentanediol and/or 1,6-hexanediol
include but are not limited to furan dimethanol: tetrahydrofuran
dimethanol; tetrahydropyran-2-methanol; levoglucosanol; and
furfuryl alcohol. Examples of byproducts which can be obtained
during synthesis of 1,5-pentanediol and/or 1,6-hexanediol include
but are not limited to isomeric hexanols; isomeric pentanols;
1,5-hexanediol; 1,2-hexanediol; 2-methyltetrahydropyran;
2,5-dimethyltetrahydrofuran; 1,2-cyclohexanediol;
1,2-cyclopentanediol; cyclohexanol, and mixtures thereof.
[0084] The .alpha.,.omega.-C.sub.n-diols obtained by the processes
disclosed herein can be converted to industrially useful materials
such as .alpha.,.omega.-C.sub.n-diaminoalkanes. For example,
1,5-pentanediol and 1,6-hexanediol can be reductively aminated to
1,5-pentanediamine (1,5-diaminopentane) and 1,6-hexanediamine
(1,6-diaminohexane), respectively, by methods known in the art.
See, for example, U.S. Pat. No. 3,215,742; U.S. Pat. No. 3,268,588;
and U.S. Pat. No. 3,270,059.
[0085] In some embodiments, the processes disclosed herein further
comprise the steps:
[0086] (c) optionally, isolating the .alpha.,.omega.-C.sub.n-diol
from the product mixture;
[0087] (d) contacting the .alpha.,.omega.-C.sub.n-diol with ammonia
and hydrogen in the presence of a reductive amination catalyst at a
temperature and for a time sufficient to form a second product
mixture comprising an .alpha.,.omega.-C.sub.n-diaminoalkane;
and
[0088] (e) optionally, isolating the
.alpha.,.omega.-C.sub.n-diaminoalkane from the second product
mixture.
[0089] In one embodiment, the .alpha.,.omega.-C.sub.n-diaminoalkane
comprises 1,6-diaminohexane. In one embodiment, the
.alpha.,.omega.-C.sub.n-diaminoalkane comprises
1,5-diaminopentane.
[0090] The reductive amination catalyst contains at least one
element selected from Groups IB, VIB, VIIB, and VIII of the
Periodic Table, for example iron, cobalt, nickel, ruthenium,
rhodium, palladium, osmium, copper, chromium, iridium, or platinum.
The elements may be in the zero oxidation state or in the form of a
chemical compound. The reductive amination catalyst may be
supported, unsupported or Raney-type. In one embodiment, the
reductive amination catalyst contains ruthenium. In one embodiment,
the reductive amination catalyst contains nickel. In one
embodiment, the reductive amination catalyst is Raney nickel. In
one embodiment, the reductive amination catalyst is Raney copper.
In one embodiment, the reductive amination catalyst is Raney
cobalt.
[0091] The reductive amination step is conducted by contacting the
.alpha.,.omega.-C.sub.n-diol, or a product mixture comprising the
.alpha.,.omega.-C.sub.n-diol, with ammonia and hydrogen in the
presence of the catalyst for a time sufficient to form a second
product mixture comprising an
.alpha.,.omega.-C.sub.n-diaminoalkane. Useful temperatures for the
reductive amination step are in the range of about 40.degree. C. to
300.degree. C., for example in the range of about 75.degree. C. to
150.degree. C. Typically pressures are in the range of about 2 MPa
to 35 MPa, for example in the range of about 4 MPa to 12 MPa. The
molar ratio of hydrogen to the .alpha.,.omega.-C.sub.n-diol is
typically equal to or greater than 1:1, for example in the range of
1:1 to 100:1, or in the range of 1:1 to 50:1.
[0092] The reductive amination step is typically performed in
liquid ammonia solvent. The ammonia is used in stoichiometric
excess with reference to the .alpha.,.omega.-C.sub.n-diol.
Typically, a molar ratio of 1:1 to 80:1 of ammonia to the
.alpha.,.omega.-C.sub.n-diol can be used, for example a molar ratio
in the range of 10:1 to 50:1. Optionally, an additional solvent
such as water, methanol, ethanol, butanol, pentanol, hexanol, an,
ester, a hydrocarbon, tetrahydrofuran, or dioxane, can be used. The
weight ratio of the additional solvent to the
.alpha.,.omega.-C.sub.n-diol is typically in the range of 0.1:1 to
5:1.
[0093] The reductive amination step can be performed in a fixed bed
reactor or in a slurry reactor, for example a batch, continuous
stirred tank reactor or bubble column reactor. The
.alpha.,.omega.-C.sub.n-diamine may be isolated from the second
product mixture by any common methods known in the art, for example
fractional distillation under moderate vacuum.
EXAMPLES
[0094] The processes described herein are illustrated in the
following examples. From the above discussion and these examples,
one skilled in the art can ascertain the essential characteristics
of this invention, and without departing from the spirit and scope
thereof, can make various changes and modifications to adapt it to
various uses and conditions.
[0095] The following abbreviations are used in the examples:
".degree. C." means degrees Celsius; "wt %" means weight percent;
"g" means gram; "mg" means milligrams; "m.sup.2/g" means square
meters per gram; "psi" means pounds per square inch; "mL" means
milliliter; "kPa" means kilopascal; "MPa" means megapascal; "GC"
means gas chromatography; "Temp" means temperature; "Ex" means
Example, "cony" means conversion; "sel" means selectivity.
Materials
[0096] All commercial materials were used as received unless stated
otherwise. 1,2,6-Hexanetriol (>=97 GC area % purity) was
obtained from Evonik DEGUSSA GmBH, Marl, Germany.
[0097] The following metal salts were used in the catalyst
syntheses described herein.
TABLE-US-00001 Metal Salt Source Rhodium (III) Chloride Hydrate
Strem Tetraammineplatinum (II) Nitrate Aldrich Copper (II) Nitrate
Hydrate Alfa Aesar Palladium Nitrate Alfa Aesar Nickel (II)
Chloride Hexahydrate Aldrich Nickel (II) Nitrate Hexahydrate
Aldrich Ammonium Perhenate Aldrich Ammonium Tungsten Oxide Hydrate
Alfa Aesar Manganese (II) Nitrate Hydrate Alfa Aesar Cobalt (II)
Nitrate Hexahydrate Aldrich Iron (III) Nitrate Nonahydrate Aldrich
Chromium (III) Nitrate Nonahydrate Aldrich
[0098] Nickel(II) chloride hexahydrate was used as the Ni salt for
the Ni-containing catalysts listed in Tables 1 and 2. Nickel(II)
nitrate hexahydrate was used as the Ni salt for the Ni-containing
catalysts listed in Table 3.
[0099] Titanium dioxide (Aerolyst 7711) was obtained from Evonik.
Zeolite Y (CBV 780) having a SiO.sub.2 to Al.sub.2O.sub.3 molar
ratio of 80:1, a nominal cation form of hydrogen, a Na.sub.2O
content of 0.03 wt %, unit cell size A=24.24, and a surface area of
780 m.sup.2/g was obtained from Zeolyst.
[0100] Percent conversion of 126HT and percent selectivity to 16HD
are defined as follows:
% Conversion = 100 * ( mol starting material charged - mol starting
material remaining ) mol starting material charged ##EQU00001## %
Selectivity = 100 * mol of product compound ( mol starting material
charged - mol starting material remaining ) ##EQU00001.2##
Synthesis of Pt/Cu/W/TiO.sub.2 Catalyst
[0101] A Pt/Cu/W/TiO.sub.2 catalyst containing 1.8 wt % Pt, 1.8 wt
% Cu, and 6.9 wt % W supported on TiO.sub.2 was synthesized using
the following procedure. Titanium dioxide (0.8842 g), which had
been ground and passed through a 400 micron mesh sieve and wetted
with 1.0 mL of water, was impregnated with 0.0396 g of
tetraammineplatinum (II) nitrate in 1.0 mL of water. The slurry was
vortexed for 15 minutes and then dried overnight under vacuum at
110.degree. C. The resulting solid was allowed to cool to room
temperature and wetted again with 1.0 mL of water, and impregnated
with a solution of Cu(NO.sub.3).sub.23H.sub.2O (0.076 g) in 1.0 mL
of water. The slurry was vortexed for 15 minutes and then dried
overnight under vacuum at 110.degree. C. The resulting solid was
allowed to cool to room temperature and wetted again with 1.0 mL of
water, and impregnated with a solution of ammonium tungsten oxide
hydrate (0.1089 g) in 3.0 mL of water. Once again, the slurry was
vortexed for 15 minutes and then dried overnight under vacuum at
110.degree. C. The resulting material was transferred to a ceramic
boat and calcined in air at 400.degree. C. for three hours.
[0102] Additional M1/M2/M3/support catalysts were prepared using
the procedure described above and the metal salts and catalyst
supports described in the Materials section. The catalysts and
their weight percentages of M1, M2, and M3 are given in Tables 1,
2, and 3.
Examples 1-29
[0103] The M1/M2/M3/support catalysts prepared as described above
were evaluated for the hydrodeoxygenation of 1,2,6-hexanetriol to
1,6-hexanediol according to the following procedure.
[0104] In each of Examples 1-29, the conversion of
1,2,6-hexanetriol to a reaction mixture comprising 1,6-hexanediol
was performed by placing approximately 1 g of an aqueous solution
of 126HT (5 wt %) and approximately 50 mg of the prepared catalyst
as indicated in Table 1, 2, or 3 with a stir bar into a 1.5 mL
pressure vessel. The vessel was charged with H.sub.2 to a
pre-reduction pressure of 145 psi (1000 kPa). The reactor was then
heated to the reaction temperature shown in Table 1, 2, or 3. The
vessel contents were stirred for 1 hour and then the pressure was
increased to 900-1000 psi (6200-6900 kPa); the reaction pressure
and temperature were maintained for 4 hours. The vessel was then
cooled to room temperature. The reaction mixture was filtered and
the product solution analyzed using GC methods. Typically, product
solutions contained 1,5-pentanediol, 1,2-hexanediol, and/or
2-hydroxymethyltetrahydropyran in addition to 1,6-hexanediol.
[0105] Results for M1/M2/M3/support catalysts wherein M1 was Pt are
presented in Table 1. Results for M1/M2/M3/support catalysts
wherein M1 was Rh are presented in Table 2. Results for
M1/M2/M3/support catalysts wherein M1 was Mn or Cr are presented in
Table 3.
[0106] In the Tables, the M1, M2, and M3 components of the catalyst
compositions are referred to as "M1 (x %)", "M2 (y %)", "M3 (z %)"
wherein x, y, and z mean the weight percentages of metals M1, M2
and M3 respectively, based on the total weight of the prepared
catalyst. For Examples 1-23, conversion and selectivity results
were calculated using uncalibrated GC peak area percentages. For
Examples 24-29, conversion and selectivity results were calculated
using calibrated GC peak area percentages.
TABLE-US-00002 TABLE 1 Conversion (Conv) of 1,2,6-Hexanetriol
(126HT) and Selectivity (Sel) to 1,6-Hexanediol (16HD) with
M1/M2/M3 Catalysts Supported on TiO.sub.2 wherein M1 is Pt; M2 is
Cu, Ni, or Pd; and M3 is Re or W. Temp M1 M2 M3 M1:M2:M3 Conv Sel
to Ex (.degree. C.) (wt %) (wt %) (wt %) Molar Ratio (%) 16HD (%) 1
180 Pt (1.8) Cu (1.8) Re (6.9) 0.09:2.8:3.7 15.2 45.1 2 180 Pt
(1.8) Cu (1.8) W (6.9) 0.09:2.8:3.7 5.9 35.9 3 180 Pt (1.8) Ni
(1.8) Re (7.3) 0.09:3.0:3.9 38.6 38.0 4 180 Pt (1.8) Ni (1.8) W
(7.3) 0.09:3.0:3.9 3.7 22.3 5 180 Pt (1.8) Pd (1.8) W (5.0)
0.09:1.7:2.7 60.1 50.5
TABLE-US-00003 TABLE 2 Conversion (Conv) of 1,2,6-Hexanetriol
(126HT) and Selectivity (Sel) to 1,6-Hexanediol (16HD) with
M1/M2/M3 Catalysts Supported on TiO.sub.2 or Zeolite CBV780,
Wherein M1 is Rh; M2 is Cu, Ni, or Pd; and M3 is Re or W. Temp M1
M2 M3 M1:M2:M3 Conv Sel to Ex (.degree. C.) (wt %) (wt %) (wt %)
Molar Ratio Support (%) 16HD (%) 6 120 Rh(1.8) Cu(1.8) Re(8.3)
1.7:2.8:4.5 zeolite 7.6 57.4 7 120 Rh(1.8) Cu(1.8) W(8.3)
1.7:2.8:4.5 zeolite 1.1 10.3 8 120 Rh(1.8) Cu(1.8) Re(8.3)
1.7:2.8:4.5 TiO.sub.2 7.8 46.0 9 120 Rh(1.8) Cu(1.8) W(8.3)
1.7:2.8:4.5 TiO.sub.2 2.5 37.8 10 160 Rh(1.8) Cu(1.8) Re(8.3)
1.7:2.8:4.5 TiO.sub.2 27.7 31.4 11 160 Rh(1.8) Cu(1.8) W(8.3)
1.7:2.8:4.5 TiO.sub.2 11.4 32.1 12 120 Rh(1.8) Ni(1.8) Re(8.7)
1.7:3:1:4.7 zeolite 9.0 52.2 13 120 Rh(1.8) Ni(1.8) W(8.6)
1.7:3:1:4.7 zeolite 1.6 9.9 14 120 Rh(1.8) Ni(1.8) Re(8.7)
1.7:3:1:4.7 TiO.sub.2 5.8 31.0 15 120 Rh(1.8) Ni(1.8) W(8.6)
1.7:3:1:4.7 TiO.sub.2 5.0 3.2 16 160 Rh(1.8) Ni(1.8) Re(8.7)
1.7:3:1:4.7 TiO.sub.2 42.6 23.4 17 160 Rh(1.8) Ni(1.8) W(8.6)
1.7:3:1:4.7 TiO.sub.2 2.8 18.5 18 120 Rh(1.8) Pd(1.8) W(6.4)
1.7:1.7:3.4 zeolite 4.5 38.2 19 120 Rh(1.8) Pd(1.8) Re(6.4)
1.7:1.7:3.4 zeolite 28.2 66.4 20 120 Rh(1.8) Pd(1.8) W(6.4)
1.7:1.7:3.4 TiO.sub.2 1.9 28.9 21 120 Rh(1.8) Pd(1.8) Re(6.4)
1.7:1.7:3.4 TiO.sub.2 34.6 56.2 22 160 Rh(1.8) Pd(1.8) W(6.4)
1.7:1.7:3.4 TiO.sub.2 23.1 30.4 23 160 Rh(1.8) Pd(1.8) Re(6.4)
1.7:1.7:3.4 TiO.sub.2 72.4 23.7
TABLE-US-00004 TABLE 3 Conversion (Conv) of 1,2,6-Hexanetriol
(126HT) and Selectivity (Sel) to 1,6-Hexanediol (16HD) with
M1/M2/M3 Catalysts Supported on TiO.sub.2 Wherein M1 is Mn or Cr;
M2 is Ni, Co, or Fe; and M3 is Cu. Temp M1 M2 M3 M1:M2:M3 Conv Sel
to Ex (.degree. C.) (wt %) (wt %) (wt %) Molar Ratio (%) 16HD (%)
24 260 Mn (1.3) Ni (0.6) Cu (4.4) 0.02:0.01:0.07 53 12 25 260 Cr
(0.4) Ni (1.6) Cu (4.4) 0.02:0.01:0.07 41 17 26 260 Mn (1.1) Co
(0.8) Cu (4.4) 0.02:0.01:0.07 44 13 27 260 Cr (0.4) Co (1.6) Cu
(4.4) 0.02:0.01:0.07 37 17 28 260 Mn (0.9) Fe (1.0) Cu (4.4)
0.02:0.18:0.07 39 12 29 260 Cr (0.9) Fe (1.0) Cu (4.4)
0.02:0.18:0.07 31 11
* * * * *